Variability of the Al26 production rate in ordinary chondrites

15 ordinary chondrites for which unusually high spallogenic $\text{Ne}{}^{22}\text{Ne}{}^{21}$ or $\text{He}{}^3\text{Ne}{}^{21}$ ratios had been reported and one meteorite with marked shock characteristics were selected in order to investigate the relations between $\text{Ne}{}^{22}\text{Ne}{}^{21}$ ratios, Al²⁶ contents and depth. We report Al²⁶ and K contents of 13 samples from 11 of these and-noble gas contents of 30 samples from all of these stones.A decrease in the Al²⁶ production rate accompanies the increase of $\text{Ne}{}^{22}\text{Ne}{}^{21}$ towards the pre-atmospheric surface: $\text{Al}{}_{\mathrm{obs}}{}^{26}\text{Al}{}_{\mathrm{calc}}{}^{26}\text{= 3.2?2.0}\text{Ne}{}^{22}\text{Ne}{}^{21}$ for $\text{1.08 ≤}\text{Ne}{}^{22}\text{Ne}{}^{21}\text{≤ 1.2}$. Large deviations from this relationship may indicate that a meteorite experienced an abnormal flux of cosmic rays.For $\text{Ne}{}^2\text{Ne}{}^{21}\text{> 1.2}$ this trend continues but the data scatter more, probably because of the steadily increasing influence of pre-atmospheric size. $\text{Ne}{}^{22}\text{Ne}{}^{21}$ ratios increase most rapidly in the outermost few centimeters according both to a plot of $\text{Ne}{}^{22}\text{Ne}{}^{21}$ vs (recovered mass)^{$\text{1}\text{3}$} and to track studies. The increase seems to derive from the enhanced importance of nuclear reactions on Si.$\text{Ne}{}^{22}\text{Ne}{}^{21}\text{< 1.08}$ defines a region where the Al²⁶ production rates are less sensitive to depth and vanish in the limit of large shielding; the weak correlation between $\text{Ne}{}^{22}\text{Ne}{}^{21}$ and Al²⁶ in this region rules out the use of the $\text{Ne}{}^{22}\text{Ne}{}^{21}$ ratio as a basis for a shielding correction to Al²⁶.     

A final summary of measurements of cosmogenic AI26 in stone meteorites

A summary is given of the final results of measurements of cosmogenic Al²⁶ activity in a total of 50 stone meteorites, mainly chondrites, carried out using coincidence gamma-spectrometry.     

柱撑剂中Al3+形态转化对柱撑蒙脱石微结构的影响

以钠基蒙脱石为原料,结合电位滴定曲线及特征临界点,将Al3+的转化划分为4种形态,并制备相应的柱撑蒙脱石。并采用X射线衍射分析、红外光谱分析及热分析对各柱撑蒙脱石进行表征,研究各柱撑蒙脱石的微结构变化及热稳定性。结果表明,Ⅲ区柱撑蒙脱石层间距d(001)值由原矿的12. 408 1 nm增加到18. 317 5 nm,同时,Ⅲ区柱撑蒙脱石Si—O伸缩振动峰强度减弱较明显,在542℃附近的蒙脱石八面体结构的脱羟基反应与原矿相比向低温区发生偏移,说明Ⅲ区柱撑蒙脱石发生了成键反应且柱撑效果最佳。     

The nature of O18/O16 and C13/C12 secular trends in sedimentary carbonate rocks

Measurements on 170 carbonate rocks show decreasing δO¹⁸ of similar magnitude for both limestones and dolomites over a time span of ~ 2800 m.y. The Proterozoic dolomites are on average heavier by ~5%. in δO¹⁸ than their coeval limestones. The data may indicate displacement in δC¹³ of about 3%. at approximately 570 m.y. ago, with Precambrian carbonates being heavier in δC¹³ at a given δO¹⁸ level than their Phanerozoic counterparts. The compilation of the previously published data is consistent with the above described features.     

Polymerization of silicate and aluminate tetrahedra in glasses,melts and aqueous solutions—II. The network modifying effects of Mg2+ , K+, Na+, Li+, H+, OH−, F−, Cl−, H2O,CO2 and H3O+ on silicate polymers

The effect of the group IA and VIIA ions, as well as Mg²⁺, and the molecules H₂O, CO₂, H₃O⁺ and OH^? on the energy of the Si-O bond in a H₆Si₂O₇ cluster has been calculated using semiempirical molecular orbital calculations (CNDO/2). Three types of elementary processes, i.e. substitution, addition, and polymerization reactions have been used to interpret data on the dynamic viscosity, surface tension and surface charge, hydrolytic weakening, diffusivity, conductivity, freezing point depression, and degree of polymerization of silicates in melts, glasses, and aqueous solutions. As a test of our calculational procedure, observed X-ray emission spectra of binary alkali silicate glasses were compared with calculated electronic spectra. The well known bondlength variations between the bridging bond [Si-O(br)] and the non-bridging bond [Si-O(nbr)] in alkali silicates are shown to be due to the propagation of oscillating bond-energy patterns through the silica framework. A kinetic interpretation of some results of our calculations is given in terms of the Bell-Evans-Polanyi reaction principle.     

Variability of the He3 and Ne21 production rates in ordinary chondrites

Al²⁶ and noble gas contents of 6 ordinary chondrites with $\text{He}{}^3\text{Ne}{}^{21}$ ratios above 6.0 or below 4.0 are used to infer the variability of the production rates of He³ and Ne²¹ (P_He³ and P_Ne²¹). The ratio of the observed Al²⁶ content to a calculated, normal value is taken as a measure of the change of P_Ne²¹ from its normal value. The corresponding change in P_He³ is then computed from the observed $\text{He}{}^3\text{Ne}{}^{21}$ ratio and an average value of P_He³.According to these calculations which exclude orbital effects, P_He³ will be near the average value in meteorites with high $\text{He}{}^3\text{Ne}{}^{21}$ ratios, while P_Ne²¹ will be about 30 per cent below normal. In meteorites with low $\text{He}{}^3\text{Ne}{}^{21}$ ratios, P_He³ may be depressed by as much as 25 per cent from normal while P_Ne²¹ may be 15–20 per cent above the average.     

Partitioning of Ni2+, Co2+, Fe2+, Mn2+ and Mg2+ between olivine and silicate melts: compositional dependence of partition coefficient

Partitioning of Ni²⁺, Co²⁺, Fe²⁺, Mn²⁺ and Mg²⁺ between olivine and silicate melts has been determined near the join (Mg_0.5·-Fe_0.5)₂SiO₄-K₂O 4SiO₂ and for seven different basaltic compositions. The experiments were made at 1 atm total pressure, 1500-1100°C, and under moderate to reducing oxygen fugacities. The concentration factor, defined as K^MO = (MO)^ol/(MO)^liq (molar ratio), increases markedly for all the cations studied as the olivine component of the liquid decreases. Much of the increase in K^MO is considered as due to the compositional effect of the coexisting liquid: the temperature effect on K^MO is probably opposite to the compositional effect (K^MO decreases as temperature decreases).The partition coefficient K^MO-MgO = (MO/MgO)^ol/(MO/MgO)^liq for the reaction, M_ol²⁺ + Mg_liq²⁺ = M_liq²⁺ + Mg_ol²⁺. is relatively constant over a wide range of SiO₂ content of the liquid, except in the case of Ni²⁺. The partition coefficients have similar ranges both in synthetic and natural rock systems: K^NiO-MgO = 1.8–3.0, K^CoO-MgO = 0.6–0.8, K^FeO-MgO = 0.27–0.38, and K^MnO-MgO = 0.23–0.32. There is a systematic variation in the partition coefficient K^MO-MgO with the composition of liquid; K^MO-MgO increases with increasing SiO₂ content of melt. The partition coefficients for Co²⁺, Fe²⁺ and Mn²⁺ are useful to test the equilibration of olivine with magma of a wide compositional range.     

溶出珊瑚砂中Ca~(2+)、Mg~(2+)的动力学实验研究及其影响因素

通过改变固液比、摇床转速、珊瑚砂粒径、温度、溶液pH值及溶液含盐量等参数,对珊瑚砂在水溶液中溶出Ca~(2+)、Mg~(2+)进行了实验,以探讨溶出过程中的动力学规律和影响因素。实验结果表明,珊瑚砂中Ca~(2+)、Mg~(2+)溶出量随反应时间逐渐增大;摇床转速越快、固液比越大、温度越高、溶液pH值越低,Ca~(2+)、Mg~(2+)溶出量越大;当珊瑚砂粒径为2.36~4.75 mm、溶液含盐量为100 mg/L时,Ca~(2+)、Mg~(2+)溶出量最大。统计分析表明,摇床转速、温度及溶液p H值均对珊瑚砂溶出有显著影响,但溶液p H值影响最大。珊瑚砂在水中的溶出过程符合收缩核内扩散模型,表明控制整个溶出过程反应速率的决定因素是内扩散速率;在15~40℃时,珊瑚砂在纯水中溶出Ca~(2+)、Mg~(2+)的活化能分别为78.07和74.91 k J/mol。     

The isotopic compositions and concentrations of lead in some chondritic stone meteorites

Microgram quantities of lead were volatilized from the chondrites Richardton, Holbrook, Beardsley and Plainview and purified for mass spectrometric analysis. Aliquots of approximately 1 μg were surface-ionized by use of the boric acid technique. The isotopic compositions found range from highly radiogenic lead in the case of Richardton to leads in the other three chondrites which are substantially less radiogenic than average lead in the crust of the earth. p]From our recent concentration determinations by the isotopic dilution method, it seems that the amount of lead in Beardsley is about 0·13 p.p.m. and that in Richardton about 0·06 p.p.m. The leads in these meteorites are consistent within a factor of approximately two with the lead-lead ages and the independently measured uranium and thorium concentrations. The lead—lead age for Richardton is the same as that found by (1955) for Nuevo Laredo, being 4·6 Æ. The lead concentration measured for Forest City is 0·09 p.p.m., while that for Holbrook is 0·28 p.p.m. Holbrook is quite anomalous in containing 2·5 times the amount of radiogenic lead that can be explained by the accumulation of decay products in situ with a primeval lead which had the isotopic composition of the lead from the troilite in the Canyon Diablo and Henbury iron meteorites. p]The total amount of lead on the surface of a meteorite appears to be comparable to the total amount inside. The isotopic composition of this surface lead indicates that it is principally terrestrial lead.     

3He/4 He比值质谱计的研制与应用

本文介绍了本课题组研制的国内第一台用于地学气体样品测定的NG-1000型3He/4He比值质谱计.该质谱计具有小的静态容积,分辨率和灵敏度高及重现性等良好的分析性能.利用该质谱计测定了我国一些地区气体样品中的3He/4He、4He/20Ne比值.所分析的3He/4He结果与VG-5400型、MM-5400型质谱计外检结果相符.     

An electrochemical study of Ni2+, Co2+, and Zn2+ ions in melts of composition CaMgSi2O6

Cyclic voltammetry has been done for Ni²⁺, Co²⁺, and Zn²⁺ in melts of diopside composition in the temperature range 1425 to 1575°C. Voltammetric curves for all three ions excellently match theoretical curves for uncomplicated, reversible charge transfer at the Pt electrode. This implies that the neutral metal atoms remain dissolved in the melt. The reference electrode is a form of oxygen electrode. Relative to that reference assigned a reduction potential of 0.00 volt, the values of standard reduction potential for the ions are $\text{E}{}^1\text{(}\text{Ni}{}^{\mathrm{2+}}\text{Ni}{}^0\text{,}\text{diopside}\text{, 1500°C) = ?0.32 ± .01}\text{V}$, $\text{E}{}^1\text{(}\text{Co}{}^{\mathrm{2+}}\text{Co}{}^0\text{,}\text{diopside}\text{, 1500°C) = ?0.45 ± .02}\text{V}$, and $\text{E}{}^1\text{(}\text{Zn}{}^{\mathrm{2+}}\text{Zn}{}^0\text{,}\text{diopside}\text{, 1500°C) = ?0.53 ± .01}\text{V}$. The electrode reactions are rapid, with first order rate constants of the order of 10^?2 cm/sec. Diffusion coefficients were found to be 2.6 × 10^?6 cm²/sec for Ni²⁺, 3.4 × 10^?6 cm²/sec for Co²⁺, and 3.8 × 10^?6 cm²/sec for Zn²⁺ at 1500°C. The value of $\text{E1}$ ($\text{Ni}{}^{\mathrm{2+}}\text{Ni}{}^0$, diopside) is a linear function of temperature over the range studied, with values of ?0.35 V at 1425°C and ?0.29 V at 1575°C. At constant temperature the value of $\text{E}{}^1\text{(}\text{Ni}{}^{\mathrm{2+}}\text{Ni}{}^0\text{, 1525°C}$) was not observed to vary with composition over the range CaO · MgO · 2SiO₂ to CaO·MgO·3SiO₂ or from 1.67 CaO·0.33MgO·2SiO₂ to 0.5 CaO·1.5MgO·2SiO₂. The value for the diffusion coefficient for Ni²⁺ decreased by an order of magnitude at 1525°C over the compositional range CaO · MgO · 1.25SiO₂ to CaO · MgO · 3SiO₂. This is consistent with a mechanism by which Ni²⁺ ions diffuse by moving from one octahedral coordination site to another in the melt, with the same Ni²⁺ species discharging at the cathode regardless of the SiO₂ concentration in the melt.     

Kinetic and thermodynamic factors controlling the distribution of SO32− and Na+ in calcites and selected aragonites

Significant amounts of SO₄^2?, Na⁺, and OH^? are incorporated in marine biogenic calcites. Biogenic high Mg-calcites average about 1 mole percent SO₄^2?. Aragonites and most biogenic low Mg-calcites contain significant amounts of Na⁺, but very low concentrations of SO₄^2?. The SO₄^2? content of non-biogenic calcites and aragonites investigated was below 100 ppm. The presence of Na⁺ and SO₄^2? increases the unit cell size of calcites. The solid-solutions show a solubility minimum at about 0.5 mole percent SO₄^2? beyond which the solubility rapidly increases. The solubility product of calcites containing 3 mole percent SO₄^2? is the same as that of aragonite. Na⁺ appears to have very little effect on the solubility product of calcites. The amounts of Na⁺ and SO₄^2? incorporated in calcites vary as a function of the rate of crystal growth. The variation of the distribution coefficient ($\text{D}$) of SO₄^2? in calcite at 25.0°C and 0.50 molal NaCl is described by the equation $\text{D = k}{}_0\text{+ k}{}_1\text{R}$ where $\text{k}{}_0$ and $\text{k}{}_1$ are constants equal to $\text{6.16 × 10}{}^{\mathrm{?6}}$ and $\text{3.941 × 10}{}^{\mathrm{?6}}$, respectively, and $\text{R}$ is the rate of crystal growth of calcite in mg·min^?1·g^?1 of seed. The data on Na⁺ are consistent with the hypothesis that a significant amount of Na⁺ occupies interstitial positions in the calcite structure. The distribution of Na⁺ follows a Freundlich isotherm and not the Berthelot-Nernst distribution law. The numerical value of the Na⁺ distribution coefficient in calcite is probably dependent on the number of defects in the calcite structure. The Na⁺ contents of calcites are not very accurate indicators of environmental salinities.     

Thermodynamic model of natural brines accounting for the presence of trace components: II. System Na+, K+, Mg2+ ‖ Cl?, Br?-H2O

This paper reports the calculations of parameters for the Pitzer equation and thermodynamic potentials of solid phases crystallizing in water-salt systems modeling chloride brines taking into account the presence of bromide ions in them. Solubility diagrams were calculated for corresponding ternary and quaternary systems containing chlorides and bromides of sodium, potassium, and magnesium at 25°C. The results of calculations are in adequate agreement with the available published experimental data on solubility and can be used to model salt crystallization during the concentration of seawater and brines. Original Russian Text ? M.V. Charykova, N.A. Charykov, 2007, published in Geokhimiya, 2007, No. 10, pp. 1129–1138.     

The determination of SO42-, NaSO4-, and MgSO40 tracer diffusion coefficients and their application to diagenetic flux calculations

Sulfur-35 was used to monitor the non-steady-state tracer diffusion of the free sulfate ion and sulfate ion-pairs in aqueous solutions of MgSO₄ and Na₂SO₄. Diffusion coefficients were derived from radiotracer flux measurements taken over ionic strengths ranging from 0.001 to 0.7. The experimental tracer diffusion coefficient is a function of the diffusion coefficients of the free sulfate ion and the sulfate ion-pairs as well as the ion pair equilibrium constant. The free sulfate ion tracer diffusion coefficient was determined independently from both the MgSO₄ and Na₂SO₄, experiments and found to be 1.11 and 1.08 (in units of 10^-5cm²sec^-1, ± 10%, respectively. These values closely agree with that calculated from the Nernst expression, 1.07 sx 10^-5cm²sec^-1. The tracer diffusion coefficients of MgSO₄⁰ and NaSO₄^- were determined to be 0.85 and 1.23 sx 10^-5cm²sec^-1, respectively. These numbers are in reasonable agreement with the earlier work on mutual diffusion coefficients by Rard and Miller (1979b) (D_MgSO4^o = 0.65, D_naso4^- = 1.19) and Harned and Hudson (1951)D_MgSO4⁰ = (0.70). A modified version of the theoretical equation developed by Pikal (1971) is proposed for predicting the tracer diffusion coefficients of many ion-pairs relevant to seawater. Many of these predicted values are found to be within 10–20% of the empirical values extracted from mutual diffusion data. The experimental and theoretical diffusion coefficient data are used to calculate revised coupled diffusion coefficients, D^g, according to the model of Lasaga (1979).     

Mg2+ removal in the system Mg2+—amorphous SiO2—H2O by adsorption and Mg-hydroxysilicate precipitation

Two chemical processes can remove Mg²⁺ from suspensions containing amorphous silica (am-SiO₂) at low temperatures: adsorption and precipitation of a Mg-hydroxysilicate resembling sepiolite. Mg²⁺ removal from am-SiO₂ suspensions was investigated, and the relative role of the two removal processes evaluated, as a function of: pH, ionic strength, Mg²⁺ concentration, and temperature.The extent of Mg²⁺ adsorption onto am-SiO₂ decreases with increasing NaCl concentration due to displacement of Mg²⁺ by Na⁺. At NaCl concentrations of 0.05 M and above, adsorption occurs only at pH values above 8.5, where rapid dissolution of am-SiO₂ gives rise to high concentrations of dissolved silica, resulting in supersaturation with respect to sepiolite. Removal of Mg²⁺, at concentrations of 40 to 650 μM, from am-SiO₂ suspensions in 0.70 M NaCl at 25 °C occurs at pH 9.0 and above. Experiments show that under these conditions adsorption and Mg-hydroxysilicate precipitation remove Mg²⁺ at similar rates. For 0.05 M Mg²⁺, at 0.70 M ionic strength and 25 °C, measurable Mg²⁺ removal occurs down to ca. pH 7.5 but is primarily due to Mg-hydroxysilicate precipitation. For the same solution conditions at 5°C, Mg²⁺ removal occurs above pH 8.0 and is primarily due to adsorption.Assuming that increasing pressure does not greatly enhance adsorption, Mg²⁺ adsorption onto am-SiO₂ is an insignificant process in sea water. The surface charge of pristine am-SiO₂ in sea water is primarily controlled by interactions with Na⁺. The principal reaction between Mg²⁺ and am-SiO₂ in marine sediments is sepiolite precipitation.The age distribution of sepiolite in siliceous pelagic sediments is influenced by temperatures of bottom waters and by geothermal gradients.     

陨石中宇宙成因核素10Be和26Al的化学分离纯化

陨石离开其小行星母体直至降到地球表面期间,受到宇宙射线的照射,产生一系列包括10Be和26Al等的放射性核素.10Be和26Al的含量及其比值记录了宇宙射线辐照历史,而陨石降落到地球表面后,它们的衰变又提供了测定其降落时间,即居地年龄的方法.10Be和拍26Al由加速器质谱测定,样品需分离纯化.为此,开展了陨石样品Be和Al的分离纯化实验.通过模拟样品的条件实验,建立了Be和Al分离纯化的化学流程,其回收率分别达到89%和70%.在此基础上,分离并测定了一个降落型普通球粒陨石(吉林陨石)非磁性部分的10Be和26Al的含量.结果显示,吉林陨石26Al/10Be的比值为5.005,远大于两者的饱和比值(2.72),说明吉林陨石经历了短期的暴露辐射,这一结果与吉林陨石第二阶段的暴露年龄0.4 Ma一致.整个化学流程的10Be/9Be和26Al/27Al空白分别为(4.33±0.46)×10-14和(6.59 ±4.66)×10-15,其中前者接近于该仪器的空白测量值,而后者则接近于仪器的检测限2.3×10-15.     

Estimation of error in the determination of Al in stone meteorites by indirect γ-ray spectrometry

The error involved in the determination of the Al²⁶ concentration by the method of Rowe and his co-workers was measured and the values they reported should be increased by a factor of 1.36 ± 0.05. The potassium contents of the meteorites measured by Roweet al., are not affected by this error and can be used with confidence.     

The 21Ne production rate in stony meteorites estimated from 10Be and other radionuclides

The ¹⁰Be contents of 28 stony meteorites with known ²¹Ne contents range from 0.97 to 23 dpm/kg and give an average ²¹Ne production rate (P₂₁) of (0.28 ± 0.02) × 10⁸ cm³ STP/g-Myr for shielding conditions corresponding to ${}^{22}\text{Ne}{}^{21}\text{Ne}\text{= 1.114}$ in an H-chondrite. Our $\text{P}{}_{21}\text{(}{}^{10}\text{Be)}$ agrees with others' P₂₁ based on ²²Na, ⁸¹Kr and ⁵³Mn but not on ²⁶A1. Temporal variations in the cosmic ray flux do not explain the disagreement satisfactorily; major errors in the radionuclide half-lives are not indicated. The discrepancy seems rooted in the data selection and the difficulties of making accurate corrections for shielding, chemical composition and other sources of variability.     

Electron paramagnetic resonance study of the site preferences of Gd3+ and Eu2+ in polycrystalline silicate and aluminate minerals

Electron paramagnetic resonance (EPR) measurements were made on Gd³⁺ and Eu²⁺ ions in polycrystalline samples to determine the nature of the sites occupied by those ions in mineral structures. Both Gd³⁺ and Eu²⁺ ions were incorporated at Ca²⁺ structural sites in β-Ca₂SiO₄, pseudo-CaSiO₃, CaMgSiO₄, CaMgSi₂O₆, hex-CaAl₂Si₂O₈, CaAl₂O₄, and Ca₃Al₂O₆. For tri-CaAl₂Si₂O₈, Eu²⁺ was incorporated at a Ca²⁺ site and Gd³⁺ was incorporated at a site where the crystalline electric field was disordered. That difference in behavior may contribute to the anomalous behavior of Eu in plagioclase feldspar. Both Gd³⁺ and Eu²⁺ were incorporated as aggregates or clusters of those ions in Mg₂SiO₄ and clino-MgSiO₃.     

铜型蛭石抗菌剂中Cu2+的赋存状态

利用天然矿物蛭石的阳离子交换特点,通过离子交换法将Cu2+植入到蛭石中,制得铜含量高达5.5%(相当于蛭石阳离子交换容量的80%)、具良好抗菌性能的铜型蛭石.经XRD、TEM、AAS分析,结合晶胞参数及晶体化学式的计算,铜型蛭石的XRD特征值更接近于标准的Mg-蛭石,这与Cu2+与Mg2+半径相近、电价相等的特点相符合.Cu2+部分以水合物的形式存在于蛭石层间,部分进入八面体中以六次配位的形式存在.铜型蛭石的a0和b0值无明显变化而c0值略有减小,这对于Cu2+的稳定是有利的.上述各特点有利于铜型蛭石抗菌剂的稳定性和持久性.